Process of printing black.



UNITED STATES Patented October 27, 1903.

PATENT OFFICE.

EDUARD ULLRIOH AND VIOTOR EUsseANcER, or HOOHsT-ON-THE-MAIN, GERMANY,Assicuoss TO FARBWERKE, VORM. MEISTER, LUOIUS & BRUNING,OF-HOOHST-ON-THE-MAIN, GERMANY, A CORPORATION.

PROCESS OF PRINTING BLACK.

SPECIFICATION forming part of Letters Patent No. 742,530, dated October27, 1903. Application file-(l August 17, 1901. Serial No. 72,356. (Nospecimens.)

To all whom it may concern.-

Be it known that we, EDUARD ULLRICH, Ph. 1)., a citizen of the Empire ofGermany, and VICTOR FUsscANcER, Ph. D., a citizen of 5 the Empire ofAustria-Hungary, residing at Hochst-On-the-Main, Germany, have inventedcertain new and useful Improvements in Processes of Printing Black, ofwhich the following is a specification.

[O The black hitherto produced by dyers or printers by oxidation orsteaming has the disadvantage that it easily turns green, as the actionof dilute acids contained in the perspiration or still more that ofreducing :5 agents, such as sulfurous acid found in the air, andespecially in storehouses, produces a greenish hue, like that ofemeraldin, the intermediate product in the formation of the black. Thisgreening often occurs to a disagreeable extent in the case of clothsdyed with anilin-black. This drawback has been avoided to a certaindegree; but an anilin-black which absolutely does not turn green has notbeen obtained hitherto. Be-

sides, the anilin-black has this drawback that cotton fiber is easilyattacked, and thus becomes rotted by the quantity of acid requisite forthe formation of the black.

We have found that primary, secondary, or tertiary amido or amido-oxyderivatives of the diphenylamin series may be substituted for the anilinin making a black and that by oxidizing these bodies on the fiber a fulldeep black may be Obtained which does 5 not become green and does notattack the fiber. The following compounds have proved specially suitablefor this purpose: paraamido-para-oxydiphenylamin, para amidopara oxyphenyltolylamin, dimethyl paraamido para oxydiphenylamin,dimethylpara-amido-para-oxyphenyltolylamin, paraamido diphenylamin, paraamidomethyldiph'enylamin, diamidodiphenylamin, diamido paraoxydiphenylamin, and dimethyl- 5 diamidodiphenylamin; and this inventionrelates to the manufacture of a black by oxidation or steaming fromthese and like bodies. Of these compounds only about one-third of thequantity necessary in the case of anilin is required for a full deepblack, and whereas in the case of anilin besides oxidizing agents acarrier of oxygen is necessary such as a solution of a vanadium salt,potassium ferrocyanid, copper sulfid, &c.-the

formation of the block occurs here so readily 5 5 that the use of acarrier of oxygen may be dispensed with, its application, however, notbeing absolutely excluded. A drawback caused by potassium ferrocyanid,which is commonly used, is avoided by this new processnamely,tl1eformation of Prussian blue, which gives to the black when it leaves thesteam a very beautiful bluish tint, which disappears, however, and,owing to the formation of hydrated peroxid of iron, gives place to aless beautiful brown-black when the goods are treated with soap andsodium carbonate. Besides, the new process has the hygienic advantage ofavoiding the vapors of prussic acid,which are evolved in the manu- 7ofacture of the black by the old process. A further drawback, due to thepotassium ferrocyanid, consists in the impossibility of printing thiscompound beside alizarin aluminium colors, as the shades of the latterare much injured by the proximity of the iron compound. As no suchcompound is used in the new process, the new black may be used togetherwith all colors Obtained by steaming. The readilyoxidizable bases usedin this process and the small quantity of acid they require to form theblack are also of specially technical value, as it allows of the colorbeing directly developed while the piece goods are passed over thedrying-cylinders immediately after padding. The slow process of dryingin the hot flue, the passing through the steam apparatus,or theprolonged spreading out in the oxidation-chamber are thus avoided.

The new black is very fast to soap, sodium carbonate, light, sulfur, andacid, as well as to alkali and ironing.

The black may be produced on half-silk and silk, as well as on cotton. 5

Examples. I Black-printing color I.-Thirty grams of para amido paraoxydiphenylamin or the equivalent quantity of any other of the aforesaidbases, one hundred grams of acetic acid of 8 Baum specific gravity,eight cubic centimeters of hydrochloric acid of 22 Baum specificgravity, six hundred grams of thickening acetate, thirty grams of sodiumchlorate, and two hundred and thirty-two cubic centimeters of water.

Black-printing color II.Thirty grams of paraamido -para oxydiphenylaminor the equivalent quantity of any other of the aforesaid bases, onehundred grains of acetic acid of 8" Baum specific gravity, thirty gramsof acetin, six hundred grams of thickening acetate, sixty cubiccentimeters of aluminium chlorate of 22 Baum specific gravity, and

one hundred and eighty cubic centimeters ofwater. After'printing thegoods are dried, steamed for three minutes, Washed, and soaped.

Padding color I.Thirty grams of paraamido-para-oxydiphenylalnin, threehundred grams of hot water, ten cubic centimeters of hydrochloric acidof 22 Baum specific gravity, fifty cubic centimeters of acetic acid of8Baum specific gravity, one hundred grains of tragacanth-water, (sixtygrams per one thousand cubic centimeters,) thirty grams of sodiumchlorate, and five hundred grams of Water.

Padding color II.-'Ihirty grains of paraamido-para-oxydiphenylamin, onehundred grains of acetic acid of 8 Baum specific gravity, thirty gramsof acetin, one hundred grams of tragacanth-water, (sixty grams per onethousand cubic centimeters,) seventy cubic centimeters of aluminiumchlorate of 22 Baum specific gravity, and five hundred grams of Water.After padding the cloth is dried in the hot flue and steamed in theMather-Flatt apparatus for three minutes, or the black is directlydeveloped on the hot drying-cylinders.

Having now described ourinvention, what we claim is- 1. The processherein described of producing a fast-black dye on the fiber, whichconsists in treating the fiber to be dyed with a diphenylamin derivativeand then oxidizing said derivative upon the fiber, substantially as setforth.

2. A fibrous material dyed with an oxidation product of a diphenylaminderivative and having the following properties: it is fast to turninggreen due to atmospheric influence to sulfurous acid, and perspiration,to reducing agents, light, boiling water, soap, feeble alkalinesolutions, alcohol, benzene, petroleum ether, ironing and to tenderingof the fiber, substantially as set forth.

In testimony that we claim the foregoing as our invention we have signedour names in presence of two subscribing witnesses.

EDUARD ULLRIOH. VICTOR FUSSGANGER.

Witnesses:

ALFRED BRISBOIS, HEINRICH HAHN.

